Methyl iodide clusters observed in gas phase by infrared cavity ring-down spectroscopy: the CH3 bending mode at 8 microm.

Infrared spectra of methyl iodide clusters produced in a supersonic jet have been observed in the CH3 bending region at 8 mum by cavity ring-down spectroscopy. The dependence of the spectral features on the mixing ratio of CH3I to He and on the stagnation pressure has allowed us to assign the absorption peaks, with the help of the previous results obtained by matrix-isolation technique [Ito et al., Chem. Phys. Lett. 343, 185 (2001)] and infrared cavity ring-down spectroscopy in the C-H stretching region [Ito et al., Chem. Phys. 286, 337 (2003)]. Ab initio calculations at the MP2 level have been carried out up to tetramer to confirm the assignments. It has been found that the frequency shifts upon clustering (relative to monomer) observed in the bending region are not monotonic, in contrast to those in the C-H stretching region. The observed frequency shifts are discussed in terms of dispersion interaction and its variation upon vibrational excitation.